Water insoluble anthraquinone dyes for cellulosic and synthetic fibers

ABSTRACT

Essentially water insoluble, non-vattable, blue to green 1nitroaroylamino-5,8-di(N-substituted)aminoanthraquinone dyes, for example, 1-(p-nitrobenzamide)-5,8-bis(p-toluidino)-anthraquinone, useful for dyeing water swellable cellulosic fibers, for example, cotton fibers, or synthetic fibers, for example, polyester fibers, or blends or mixtures thereof, said dyed fibers being fast to light, washing, drycleaning and sublimation.

United States Patent 1 McGuire 1 Sept. 18, 1973 WATER INSOLUBLE ANTI-IRAQUINONE DYES FOR CELLULOSIC AND SYNTHETIC FIBERS [75] Inventor: Thomas Michael McGuire, Newark,

Del.

[73] Assignee: E. I. du Pont de Nemours and Company, Wilmington, Del.

[22] Filed: July 30, 1971 21 Appl. No.: 167,828

[52] US. Cl. 260/377, 8/21 B, 8/21 C, 8/24, 8/25, 8/39, 8/40, 260/207, 260/207.l,

[5 l] Int. Cl C09h H42 [58] Field of Search 260/377, 372, 207.1

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 1,147,110 4/1969 Great Britain 260/372 Primary Examiner-Lorraine A. Weinberger Assistant ExaminerE. Jane Skelly Attorney-Louis H. Rombach [5 7 ABSTRACT 7 Claims, No Drawings WATER INSULUBLE ANTHRAQUINONE [)YES FOR CELLULOSIC AND SYNTHETIC FIBERS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to water insoluble anthraquinone dyes which have utility in the dyeing of a broad spectrum of synthetic and natural materials, especially water swellable cellulosic materials, or mixtures or blends of such synthetic and natural materials.

2. Description of the Prior Art It is well known in the art that synthetic fibers, for example, fibers prepared from polyesters, polyamides or cellulose acetate, can be dyed with a wide variety of disperse dyes whose solubilities in water vary from very low to moderately high.

Natural fibers such as water swellable cellulosic fibers, especially cotton, are dyed by processes, and with dyes, which usually differ markedly from the processes and dyes employed with synthetic fibers. The conventional methods for dyeing water swellable cellulosic materials may be summarized as follows:

1. A high molecular weight water insoluble dye is formed within the material, either by reacting two smaller components, as in the formation of an azoic dye by a coupling reaction, or by a chemical reaction which renders insoluble a soluble dye precursor, as in vat and mordant dyeing.

2. A water soluble preformed dye having an affinity for the cellulosic material is exhausted onto the material from an aqueous solution by a procedure which involves reducing the solubility of the dye in the aqueous solution, as with direct dyes.

3. A dye containing a substituent which reacts with the cellulose or a modified cellulose is exhausted onto the material from either an aqueous or nonaqueous solution under conditions such that the dye is chemically bonded to the substrate, as with fiber reactive dyes.

4. Water insoluble pigments are bonded to the cellulose with polymeric materials, as in pigment printmg.

5. A finely divided form of a water insoluble dye is incorporated into the cellulose during a manufacturing step, as is sometimes done during spinning of viscose rayon.

None of these conventional procedures can be used to dye water swellable cellulose by directly introducing into the material a preformed, nonreactive, water insoluble dye since such dyes have little natural affinity for or substantivity to such cellulosic materials.

Representative of the aforesaid processes wherein dyes are formed in situ after a precursor is deposited on or within the cellulose are processes disclosed in US. Pat. Nos. 396,692 and 2,069,215 and British Pat. No. 1,071,074. A process employing water soluble preformed dyes for dyeing cellulose is discussed in the Journal of the Society of Dyers and Colourists, 73, 23 i957).

The aforesaid processes suffer from a variety of disadvantages, such as complexity of application, inability to achieve a broad spectrum of colors, and low fastness of the dyed cellulose to aqueous washing and/or drycleaning with organic solvents.

The use of dyes of low water solubility for dyeing cotton is disclosed in British Pat. No. 1,1 12,279. The process involves the application of dye, water and urea or a structurally related compound to the substrate, followed by heating. in such a process dye utilization frequently is poor and undesirable basic degradation products from the urea or related compound may be formed.

Problems in addition to the above are encountered in the use of prior art dyes and dyeing processes for blends or mixtures of water swellable cellulosic and synthetic materials. Generally, complex two-stage processes are required and the components of the blend or mixture are dyed in separate steps with different dyes. Cross-staining may result and the amounts of dyes required usually are high, with each component undesirably interfering with the dyeing of the other. When cross-staining occurs, the dye must be capable of being scoured off the stained component. Even under optimum conditions, however, shade match on both components of the blend is difficult to achieve. The complexity of the two-stage process for dyeing blends also is apparent from a consideration of the divergency of operating conditions between conventional dyeing processes for water swellable cellulosic materials and synthetic materials. in contrast to the aforesaid procedures for dyeing water swellable cellulose, the usual proce dures for dyeing synthetic materials are based on dissolution of water insoluble dyes in the synthetic material.

Representative of prior art on the dyeing of blends of such cellulosic and synthetic materials employing a two-stage process is US. Pat. No. 3,313,590. Analogous to the dyeing of such blends and confirming the aforesaid distinction between water swellable cellulosic materials and non-water swellable cellulose acetate, US. Pat. No. 3,153,563 discloses a two-stage process wherein the cellulose acetate is dyed with a water insoluble dye without coloring the cellulose which then is dyed in an independent step.

The swelling of cotton fibers and other similar cellulosic materials by water has long been known. Swelling usually is rapid upon contact with water, but it is facilitated by wetting agents and by heat. The swollen materials are enlarged, more flexible, reduced in strength, and otherwise modified in physical and mechanical properties. Because of their open structure, swollen cellulosic materials can be penetrated by and reacted with low molecular weight water soluble compounds. Valko and Limdi in Textile Research Journal, 32, 331-337 (1962) report that cotton can be swollen with water containing both high boiling, water soluble, nonreactive compounds of limited molecular weight and a crosslinking agent. The water can be removed with retention of swelling and cross-linking can then be effected. The authors suggest that the technique may be useful not only for the introduction into cotton of water soluble reactive materials (crosslinking agents) but also other reactive materials which are insoluble in water but soluble in said high boiling, water soluble. nonreactive compound. A similar technique is described in US. Pat. No. 2,339,913 issued Jan. 25, 1944 to Hanford and Holmes. The cellulosic is swollen with water, the water then is replaced with methanol-benzene and finally with benzene, with retention of swelling. A cellulose-reactive material (cross-linking agent) is added as a benzene solution and crosslinking is effected.

Blackwell, Gumprecht and Starn in Canadian Pat. No. 832,343 disclose a process for dyeing water swellable cellulosic materials with preformed disperse dyes, that is, dyes which do not require an in situ chemical reaction, such as oxidation or reduction, for developent of color on the substrate, such as a fabric, which process comprises contacting the water swellable cellulosic material in any sequence with the following:

1. water in an amount sufi'icient to swell the cellulose; 2. a preformed dye in an amount sufficient to color the cellulose, a boiling saturated solution of which dye in 0.1 Molar aqueous sodium carbonate exhibits an optical absorbance not in excess of about 30; and 3. a solvent in an amount sufficient to maintain swelling of the cellulose if water is removed, and which a. is at least 2.5 weight percent soluble in water at 25C., b. boils above about 150C. at atmospheric pressure, c. is a solvent for the dye at some temperature in the range of about to 225C, and d. has the formula wherein n is 0 or 1;

m is a positive whole number;

wherein R is C alkyl, C cycle-alkyl, C aralkyl or alkaryl, C aryl, C aryl, or furfuryl;

R is -OH, -OR -SR -NHR -NR (C,. alkyl), NR (C-,., aralkyl or alkaryl),

-NH(naphthyl), wherein R is as defined above;

x is the number of unsatisfied valencies in A; and V A B O QH CHORCH -CH CHORCH CH C(CH OR) (-Cl-l C(Cl-l OR)- (CH CCH- 0R, (-CH C, CH (CHOR),,CH OR, -CH (CHOR- ),,CH or -Cl-l (CHOR),,.,(CH),-CH in which y is 2, 3 or 4; z is 0, 1, 2, 3 or 4 but no greater than y; and R is as defined above;

provided that at some stage during the process the interior of the swollen cellulose is contacted with a solution of the preformed dye in aqueous solvent or solvent.

Particular embodiments of the aforesaid process include those wherein said solution is formed within and- /or outside the swollen cellulose and those wherein solution of dye in aqueous dye solvent or dye solvent is achieved by means of heat, by reducing the proportion of water to dye solvent, or by adding an auxiliary solvent. Embodiments of the process also include dyeing at elevated temperatures.

Still other embodiments of the aforesaid process include the dyeing of blends or mixtures of cellulosic and synthetic materials, such as polyamide or polyester, with the same dye. In such a process the cellulose is dyed as described above and the synthetic material is dyed either at the same time or in an independent step of the process.

WW X

RNH O I ll | l RNH O l 5 wherein R is aryl.

OBJECTS AND SUMMARY OF THE INVENTION It is an object of this invention to provide water insoluble blue to green anthraquinone dyes which are useful in the above-described process of Blackwell et al. for dyeing water swellable cellulosic materials and blends or mixtures thereof with synthetic materials. It is a further object to provide dyes which give a good balance of shade when used to dye the aforesaid blends or mixtures. Another object is to provide dyes which exhibit good fastness to light, washing, drycleaning and sublimation when applied to water swellable cellulosic materials, synthetic materials or blends or mixtures of such cellulosic and synthetic materials. Still another object is to provide water insoluble anthraquinone dyes which are useful for dyeing synthetic materials by conventional procedures.

In summary, the present invention resides in the discovery of blue to green anthraquinone dyes having the 35 formula SO NH SO NHalkyl, SO NHR, SO N(alkyl) SO N(alkyl)R, COalkyl, COR, CO alkyl, CO R, SO alkyl, R or N=NR, wherein DETAILED DESCRIPTION OF THE INVENTION The aforesaid anthraquinone dyes of this invention can be prepared by conventional processes and techniques. As an example of such processes and techniques, an aromatic or aliphatic amine, such as listed in Tables 1 and 2, respectively, can be condensed with 5- aminoquinizarin or l,4,5-triaminoanthraquinone. Both are art-known compounds. The reaction can be carried out by reducing either of the aforementioned anthraquinone derivatives wholly or partially to the leuco form in known fashion and heating the resulting material with at least two moles of the amine in a suitable solvent. For arylamines the reaction is carried out in the presence of boric acid. Suitable solvents include chlorobenzene, Cellosolve, l-pentanol or an excess of the amine itself. Zinc and hydrochloric acid can be used as a reducing agent by adding them directly to the reaction mixture. Alkylamines can be condensed with S-aminoquinizarin or l,4,S-triaminoanthraquinone in aqueous alcoholic media in the presence of sodium carbonate or sodium hydroxide. Sodium hydrosulfite is commonly used as the reducing agent in these systems. The leuco form of the product is then oxidized in each case by prolonged heating of the reaction mixture in air, advantageously in the presence of an aromatic nitro compound. The resulting l-aminor5,8-di(substituted amino)anthraquinone is then condensed by known procedures with mor p-nitrobenzoyl chloride to give the desired dye.

TABLE 1 di-n-hexylamine di-n-nonylamine cyclohexylamine 4-n-octylcyclohexylamine TABLE 2 n-hexylamine n-dodecylamine n-octadecylamine di-n-propylamine m-aminobenzotrifluoride 2,5-or 3,5-dichloroaniline aniline mor p-toluidine p-n-octylaniline p-n-dodecylaniline 0-, mor p-anisidine o-, mor p-phenetidine p-butoxyaniline or 3,5-xylidine 5-chloro-2-methylaniline 2,4-, 2,5-, or 3,5-dimeth- 2-chloro-S-methoxyaniline oxyaniline 5-chloro-2-methoxyaniline 3,4-diethoxyaniline 4fluoro-2-methylaniline cresidine 5-fluoro-2-methylaniline 4-fluoro-2,S-dimethoxyaniline p-aminoacetophenone p-octylsulfonylaniline m-aminobenzoic acid, propyl ester p-aminobenzophenone 4-amino-3-bromobenzophenone 4-amino-4-nitrobenzophenone p-aminobenzoic acid, pchlorophenyl ester 4-(p-butoxyphenylsulfonyl)- 3-isopropyl-4-anisidine 0-, mor p-chloroaniline 0-, mor p-bromoaniline 5-chlore-2,4-dimethoxyaniline p-aminoacetanilide p-aminododecanoylanilide 4'-aminobenzanilide 3'-amino-4-t.-butylbenzanilide p-aminobiphenyl m-phenoxyaniline Q-ethylaniline p-phenoxyaniline 2,5-dimethoxy-4-( phenylsulm-cyanoaniline fonyl )aniline p-(phenylazo)aniline 3-amino-5-chlorobenzamide 4-(p-nitrophenylazo)-2- anthranilic acid, N-n-octylamide methoxy-S-methylaniline p-aminobenzoic acid,

N,N-di-ethylamide 2toluidine-4-(N- butylsulfonamide) 2-anisidine-5-(N,N-dirnethylsulfonamide) 5-amino-2-chlorobenzanilide p-aminobenzoic acid,

N-methyl-anilide p-aminobenz( pn-hexylanilide) orthanilamide sulfanil-( p-anisidide) metanil-(N-butylanilide) As a further example of conventional processes and techniques, the dyesof this invention can be obtained by the reaction between an aromatic amine, such as given in Table 2, and l-acylamino-5,8- dihaloanthraquinone. Aliphatic amines do not readily undergo bis-condensation with these materials. Either the chloroor bromoanthraquinone can be used, but the chloro compound is preferred for economic reasons. The reaction is carried out by heating the reactants together in a suitable solvent, such as nitrobenzene, o-dichlorobenzene or an excess of the amine itself. It is advantageous to have an inorganic acid acceptor present, such as an alkali metal acetate or carbonate or a mixture thereof. Copper or a copper salt or a mixture thereof may be added to promote the reaction if desirable. The l-acylamino-S ,8- dichloroanthraquinones can be obtained by acylating l-amino-5,8-dichloroanthraquinone in known fashion with mor pnitrobenzoyl chloride. Alternatively, acylation of the l-amino group can follow the biscondensation reaction with an aromatic amine. l- Amino-5,8-dichloroanthraquinone canbe obtained by treating l-aminoanthraquinone with chlorine in concentrated or fuming sulfuric acid in the presence of a catalyst such as iodine. Chlorine is passed through the reaction mixture at about 25-80C. until' the amount of the desired product is at a maximum as shown, for example, by thin layer or vapor phase chromatography. In practice, a mixture of compounds is obtained, the mixture containing small amounts of unreacted starting material, monoand trichlorinated compounds, and other dichloro isomers. Purification of the l-amino- 5,8-dichloroanthraquinone is best carried out after reaction with mor p-nitrobenzoyl chloride by recrystallization from a suitable solvent, such as odichlorobenzene. The trichlorinated material l-amino- 4,5,8-trichloroanthraquinone is the most difficult to remove. However, it has been found that minor amounts of this material, up to about 30 weight percent, in the 'l-acylamino-5,8-dichloroanthraquinone provide a mixture of dyes upon reaction with the amine, as described above, the properties of which mixture are comparable to those of the dye obtained from the pure dichloro intermediate. In certain cases it has been found that the dye mixture exhibits a crockfastness, when applied to cellulose-polyester blend fabrics by the process of Blackwell, et al., which is superior to that obtainedwhen the pure dye is employed. There is, of course, an

obvious economic advantage in not having to effect a separation of the dichloro and trichloro intermediates prior to the dye-forming step.

Dyes prepared from the aliphatic amines of Table l are greenish blue. Those made from the aromatic amines of Table 2, except for the monoazo amines, are green. Monoazo amines produce yellowish green shades.

Greenish blue dyes having the above formula wherein X is NI-IR and R is wherein R is (1 alkyl and R is H or C alkyl can be obtained by condensing 1,4-diamino--nitroanthraquinone with a bromophenyl derivative, such as l-bromo-2,4,6- trimethylbenzene, l-bromo-2,4 ,6-triethylbenzene, 2-bromo-l ,3-dimethylbenzene or 2-bromo- 1 -ethyl-3,5- dimethylbenzene. The condensation is carried out as described in the prior art, for example, by heating the reactants together in an inert organic solvent in the presence of an acid acceptor, such as an alkali metal carbonate or acetate. Copper or a salt thereof can be added to accelerate the reaction. The resulting 1,4- bis(alkylanilino)-5-nitroanthraquinone then can be reduced by known procedures to the S-amino derivative and acylated with mor p-nitrobenzoyl chloride to give the desired dye.

The cellulosic materials which can be dyed with the dyes of this invention by the previously described Blackwell et al. process include all forms of cellulose which increase in size and in flexibility upon exposure to water. Suitable materials include natural fibers and purified wood pulps as well as reconstituted cellulose in fiber and film form. Cotton fibers can be dyed in any of the forms in which they are conventionally used in textile materials and after any of the treatments conventionally used to prepare them for dyeing. Also included is cotton which has been treated in any way which does not significantly reduce its swelling upon heating with water; raw or scoured cotton and cotton which has been mercerized or otherwise preshrunk are dyeable. Reconstituted cellulosic fibers which are sufficiently open in structure so that they are swollen by water and penetrated by a dye solvent are dyeable, for example, cuprammonium rayon. Xanthate viscose rayon normally has a structure which is more difficult to swell and may require exposure to dye, water, and dye solvent for somewhat longer times at lower temperatures. To facilitate dyeing, such fabrics can be pretreated with ID percent aqueous caustic or the dyeing can be carried out in the presence of wetting agents, preferably of the nonionic type. Mixtures of cotton and rayon fibers can be dyed, and the dyes employed herein also can be used to dye purified wood pulp and paper. Excluded as the water swellable cellulosic material, as considered herein, is cellulose acetate which does not exhibit the requisite swellability in the presence of water.

The synthetic materials which can be dyed with the dyes of this invention include polyesters, polyamides, cellulose ethers and esters, and copolymers and mixtures thereof with other components intended to make them more easily dyeable or to add other desirable properties. Many of the aforesaid dyes can be applied to synthetic materials by a conventional Thermosol dyeing procedure.

The dyes of this invention can be applied to water swellable cellulosic materials, or to blends or mixtures thereof with synthetic materials, by the abovedescribed Blackwell et al. process. The dyes of this invention are particularly useful for dyeing mixtures and blends of cotton and polyester or polyamide, such as mixtures containing 50 to 80 percent polyethylene terephthalate and 20 to 50 percent cotton. in such mixtures, the synthetic material is dyed using conventional process conditions. Since the dyes of this invention can be used to dye both components in a blend of mixture, scourability as a factor in dye selection is avoided since the previously described cross-staining problem has been minimized.

The dyes of this invention dye the substrate directly, that is, they do not require oxidation, reduction, hydrolysis, or any other chemical modification for development of color or fastness. The dyes exhibit little difference in shade or polyester and cotton and hence an excellent balance of shade and strength can be achieved on blend fabrics of these materials. The dyes exhibit excellent fastness to washing, drycleaning, sublimation and light. Many can be isolated in highly crystalline form and can be milled easily to fine aqueous dispersions. Others, particularly those containing long chain alkyl groups, are obtained as low melting solids or oils.

In dyeing cellulosic materials with the dyes of this invention using the Blackwell et al. process, water, dye, and dye solvent can be applied to the substrate in any sequence as long as water and dye solvent are simultaneously present at some stage which is either before or simultaneous with actual dyeing. The preferred method for dyeing fabrics composed of cellulosic fibers or mixtures of cellulosic and synthetic fibers is to impregnate the fabric with a mixture of one or more dyes, water, and dye solvent in a conventional dye padbath followed by squeezing to remove excess dye liquor, or to print with a solvent-containing printing paste, and subsequently heating to evaporate sufficient water to effect dissolution of the dye, at which time the fabric is dyed. Alternatively, water is evaporated, but in an insufficient amount to effect dissolution of the dye, after which pressure and heat are applied to effect dissolution without further evaporation of water. Dye pastes can be prepared by conventional techniques such as by milling the dye in the presence of a dispersing agent or surfactant. A dyebath can be prepared by diluting the dye paste with water or with aqueous solvent. Addition of a solvent to the dye paste before addition of water may cause dye separation and usually is avoided. It will be understood by those skilled in the art that additives other than a dye solvent and a dispersing agent can be present in dyebaths. Such additives frequently include migration inhibitors such as purified vegetable gums and wetting agents, examples of which are ionic and nonionic surfactants such as ethylene oxide condensation products, hydrocarbon sulfonates and long-chain alcohol sulfates. Dye-baths used in practicing this invention also can contain dyes other than those of this invention; for example, direct dyes or fiber reactive dyes for cotton or for polyamides can be present for shading purposes.

In the preferred dyeing procedure with the dyes of this invention, an aqueous dye dispersion and the organic solvent are applied to the fabric from a single padbath. The amount of water in the padbath usually is -95 weight percent and the solvent, 5-30 weight percent. The padded fabric is heated at l225C. for 30-180 seconds. For cotton, temperatures as low as C. usually are adequate. The dyed fabric generally is given an aqueous scour, or an aqueous scour followed by a perchloroethylene scour, to ensure complete removal of surface dye.

The dyes of this invention which cannot be obtained as aqueous dispersions can be employed as solutions in the hot solvent. Alternatively, the dye can be employed as a solution in a low boiling auxiliary solvent, as defined by Blackwell et al., such as a halogenated hydrocarbon boiling below about 130C.

The following demonstrates the advantage of using the dyes of this invention in the Blackwell et al., process, as opposed to conventional vatting procedures, in the dyeing of cotton. A piece of cotton poplin was padded with an aqueous bath containing 50 grams per liter of a 15 percent aqueous dispersion of the dye of Example l (A). Pickup was 50-60 percent. The fabric was dried and then padded with an aqueous solution containing caustic soda (45 grams per liter) and sodium hydrosulfite (45 grams per liter). The cloth was steamed for 30 seconds at 104C. and rinsed. The cotton was then treated for minutes in an aqueous solution of sodium perborate (25 grams per liter) at 49C. Next, the material was soaped for 5 minutes at 93C. in 2 percent oleate soap solution, rinsed thoroughly and dried. Finally, the green tinted material was scoured in perchloroethylene at 50C for 5 minutes. Almost all of the color was removed from the fabric. In contrast to this as shown below in Experiment E, deep green shades, fast to the perchloroethylene scour, were produced when the dye was applied by the Blackwell et al. process.

The following experiments demonstrate the utility of the dyes of this invention.

Dyeing 65/35 Dacron Polyester/Cotton Blend Fabric A. A padbath was prepared from:

an aqueous green dye paste active ingredient) containing A continuous length of 65/35 Dacron polyester/cotton fabric was padded at 60 percent uptake, based on the weight of the fiber, and the padded fabric was passed at a rate of 2 yards per minute between two 1,000 watt infrared lamps (Fostoria-Fannon, Inc., Infrared Heater Model 6624), with each lamp shining on opposite surfaces of the fabric from a distance of about 3 inches. The continuously moving fabric was passed through a circulating air oven at 80l00C., with a hold-up time of 1 minute, and then through an oven at 200210C. with a hold-up time of 1.7 minutes. The hot dry fabric was cooled to room temperature and rinsed for one minute each in sequence: inwater at -30C., in water at 9095C., at 90-95C. in water containing 1 percent of an ether-alcohol sulfate detergent, in water at 90-95C., and in water at 20-30C. The material was dried, then scoured for 5 mins. in perchloroethylene at 50C., and dried again. The fabric was uniformly colored in deep green shades of good balance and fastness properties. B. Experiment A was repeated except that the heating was carried out as follows. The padded fabric was passed at a rate of 2 yards per minute between banks of infrared lamps, with one 1,000 watt lamp (Fostoria- Fannon, lnc., Infrared Heater Model 6624) shining on each surface perpendicular to the fabric from a distance of about 3 inches. The moist fabric was then passed over a series of four revolving smooth-surfaced drums increasing stepwise in temperature from 100C. to about 150C. The average contact time on each drum was about 18 seconds. Next, the fabric moved continuously into an oven held at about 210C. where the total contact time was about 90 seconds.

C. Experiment A was repeated except that the dye of Example 5 was employed. The fabric was uniformly dyed a deep greenish blue shade of good balance and fastness properties.

D. Experiment C was repeated except that the heating was carried out as in Experiment B. Similar results were obtained.

Dyeing Cotton Broadcloth E. Experiment A was repeated except that a 100 percent mercerized cotton broadcloth was employed, the amount of glycol, Carbitol and boric acid each was increased 50 percent, and the maximum temperature was reduced to about 180C. The cotton cloth was dyed a deep, uniform green shade of good fastness.

F. Experiment B was repeated employing the modifications recited in Experiment E. Similar results were obtained.

Printing of 100 percent Cotton Fabric G. A cotton fabric was padded to about percent pickup with an aqueous solution containing 200 grams per liter of polyethylene glycol (M.W. 350). The padded fabric was heated at 160C. for 5 minutes to evaporate water. The fabric was then printed in a pattern with a print paste prepared from:

an aqueous green paste (15% active The printed fabric was heated at lC. for seconds, scoured in water containing an ether-alcohol sulfate detergent at about 90C., for 5 minutes, dried, scoured in tetrachloroethylene at about 50C. for 5 minutes and dried. The printed areas were strongly dyed in a green shade.

Printing of 65/35 Dacron Polyester/Cotton Blend Fabric H. Experiment G was repeated except that a 65/35 Dacron polyester/cotton fabric was employed, the glycol was reduced to grams per liter, and the maximum temperature was increased to 200C.

Dyeing of Dacron Polyester The dyes of this invention can be applied to synthetic fibers by a conventional pad-heat procedure. The following experiment shows the amenability of these dyes to the Thermosol process.

'1. Dacron polyester fabric was immersed for fifteen minutes at 82C. in an aqueous bath containing 1 percent ether-alcohol sulfate surface active agent and 1 percent tetrasodium pyrophosphate. The fabric was rinsed in cold water, then padded at 40-50 percent pickup, based on dry fabric weight, in a dyebath prepared from:

an aqueous green dye paste 15% active ingredient) containing the dye of Example 3 50 grams purified natural gum ether thickener 20 grams water to 1 liter The padded material was passed through an infrared predryer, then heated to and held at 213C. for 90 seconds. The fabric was rinsed in water at 27C., scoured for minutes at 93C. in water containing 1 percent ether-alcohol sulfate detergent, rinsed in water at 27C. and dried. The polyester fabric was dyed a deep green shade.

Further to the above, when the procedures of Experiments A and E were employed to dye polyester/cotton blend fabrics with the dyes of Examples l(A), l(B), 2, 3, 4 and 5, dyeings of excellent fastness to light, washing and sublimation were obtained. The fast'ness to crocking with the dye of Example l(B) was slightly inferior to that with the dye of Example l(A).

The following examples illustrate the preparation of the dyes of this invention. Parts are given by weight unless otherwise indicated.

EXAMPLE 1 (A) A mixture of 29.2 parts of l-amino-5,8- dichloroanthraquinone containing a minor amount of l-amino-4,5,8trichloroanthraquinone, 260 parts of odichlorobenzene and 22.3 parts of p-nitrobenzoyl chloride was stirred under a nitrogen sweep at 140C. for 2 hours and then allowed to cool to room temperature. The solids were isolated by filtration, washed successively with methanol, hot water, percent aqueous sodium carbonate solution, hot water (until free of a1- kali) and finally with methanol, and dried. Yield of l- (p-nitrobenzamido)-5,8-dichloroanthraquinone: 23.3 parts; m.p. 286-298C.

A mixture of 218 part of the aforesaid l-(p-nitrobenzamido)-5,8-dichloroanthraquinone, 214 parts of p-toluidine, 98.4 parts of anhydrous sodium acetate, 127.2 parts of anhydrous sodium carbonate and 2,000 parts of nitrobenzene was stirred at 190C. for 20 hours. The charge was allowed to cool to 90C., whereupon 800 parts of ethanol were added. The mass was allowed to cool to room temperature with stirring and the solids were isolated by filtration. After washing several times with methanol and then with hot water, the solids were reslurried in dilute sulfuric acid and isolated by filtration. The dye was washed with hot water, until the washings were neutral, and then dried. Yield: 248 parts; m.p. 262265C. An absorption spectrum of the dye in the visible region exhibited a shoulder at 625 m;r(a,,,,,, =26.8 liters gmfcmf) and a peak at 665 mu (a,,,,,, 30.6 liters gm."cm.). Thin layer chromatography indicated the presence of a minor amount 10-15 percent) ofa yellowish green component in the green product. Based on the above, the main component is 1-(p-nitrobenzamido)-5,8-bis(p-toluidino)- anthraquinone. The minor component was shown to be l-( p-nitrobenzamido )-4,5 ,8-tris( ptoluidino)anthraquinone by chromatographic comparison with an authentic sample thereof.

(B) A sample of the dye mixture from (A) was recrystallized from chloroform. Thin layer chromatography indicated the removal of much of the l-(pnitrobenzamido)-4,5,8-tris(p-toluidino)- anthraquinone from the mixture, leaving a significantly purer sample of 1-(p-nitrobenzamido)-5,8-bis(ptoluidino)anthraquinone, m.p. 290-29lC. The dye exhibited absorptivities of 31.3 liters gm."cm.' at 625 my. (shoulder) and 35.5 liters gmfcmf' at 664 mp. (peak).

Green dyes of similar dyeing and fastness properties can be prepared by the above procedures by replacing p-toluidine with molar equivalent quantities of aniline, o-toluidine, m-toluidine, o-anisidine, m-anisidine or panisidine.

EXAMPLE 2 A mixture of 5 parts of 1 -(p-nitrobenzamido)-5,8- dichloroanthraquinone, 36 parts of m-chloroaniline, 2.46 parts of anhydrous sodium acetate and 3.18 parts of anhydrous sodium carbonate was stirred at 190195C. under a nitrogen flow for 25 hours. The charge was cooled to C. and 25 parts of ethanol were added. After allowing the reaction mixture to cool to room temperature, the solids were isolated by filtration and washed with ethanol and then with water. The solids were then reslurried in dilute sulfuric acid, stirred at 80C. for 1 hour, isolated by filtration, washed successively with water (until free of acid) and finally with ethanol, and dried. Yield: 5.5 parts. Thin layer chromatography indicated a minor amount of a yellowish green impurity in the bluish green product. The impurity was shown by chromatographic comparison with an authentic sample to be l-(pnitrobenzamido )-4,5 ,8-tris( m-chloroanilino anthraquinone. Traces of other impurities were removed by extraction with boiling chloroform. The purified dye mixture had a m.p. of 3l2-316C. and exhibited absorptivities of 21.1 liters gm. cm. at 612 my. (shoulder) and 24.0 liters gm. cm. at 655 my. (peak). Based on the above procedure and the chromatographic evidence, the mixture consists of about percent of 1-(p-nitrobenzamido)-5 ,8-bis( mchloroanilino)anthraquinone and about 15 percent of 1-(p-nitrobenzamido)-4,5,8-tris(m-chloroanilino)- anthraquinone.

Dyes of similar dyeing and fastness properties can be prepared by the above procedures by replacing mchloroaniline with molar equivalent quantities of mtrifluoromethylaniline, 3-chloro-2-methylaniline or 5-chloro-2-methoxyaniline.

EXAMPLE 3 Zinc dust (8.91 parts) was added slowly to a mixture of 34 parts of l,4,5-triaminoanthraquinone, 435 parts of p-n-butylaniline, 38.2 parts of boric acid and 48.5 parts of concentrated hydrochloric acid, which mixture was being stirred under nitrogen at 75C. The reaction mixture was then heated to C. with stirring for 4 hours, after which it was allowed to cool to below 100C. Next, 61.2 parts of pulverized potassium hydroxide were slowly added and the reaction mass was allowed to cool to 65C. After adding parts of methanol, the mixture was stirred overnight and the solids were isolated by filtration, washed with methanol and then with hot water, until the washings were neutral, and dried. Yield of 1,4-bis( p-n-butylanilino)-5- aminoanthraquinone: 46.5 parts; m.p. 125l31C. Thin layer chromatography using as eluent a 1:19 mixture of acetonitrile and benzene) indicated the green product was almost free of colored impurities.

A mixture of 45 parts of the above anilinoanthraquinone and parts of nitrobenzene was heated under a nitrogen purge at 120C. wth stirring for 30 minutes to remove traces of water from the charge. Next, 16.3

parts of p-nitrobenzoyl chloride were added slowly and the mixture was stirred for 1 hour at 120C. After cooling the reaction mass to about 90C., 120 parts of ethanol were added and the mixture was allowed to cool with stirring overnight. The solids were isolated by filtration, washed with methanol, and then with hot water and finally with methanol, and dried. The green dye product melted at 143-l46C. and exhibited absorptivities of 28.5 liters gmfcm? at 624 my. (shoulder) and 32.2 liters gm." cm. at 663 mp. (peak). Thin layer chromatography (acetonitrile:benzene 1219) showed the dye to be in a high state of purity. Based on the above, the dye is 1-(p-nitrobenzamido)-5,8-bis(pn-butylanilino)anthraquinone.

EXAMPLE 4 The first part of Example 3 was repeated, except that the 435 parts of p-n-butylaniline were replaced by 330 parts of mixed xylidines. The yield of product was 41.3 parts; m.p. 154160C.

The second part of Example 3 was repeated, except that the 45 parts of the anilinoanthraquinone intermediate were replaced by 40 parts of the above xylidinoanthraquinone intermediate. The resulting chromatographically pure green dye (43.5 parts) had a m.p. of 204-207C. and exhibited absorptivities of 29.3 liters gm.cm. at 620 mp. (shoulder) and 33.4 liters gm. cm. at 655 mp. (peak). Based on the above, the dye is 1-(p-nitrobenzamido)-5,8- bis(xylidino)anthraquinone EXAMPLE A mixture of 25.5 parts of S-aminoquinizarin, 4 parts of caustic soda, 120 parts of isopropanol and 50 parts of water was heated to the reflux temperature under nitrogen. Next, l7.4 parts of sodium hydrosulfite were added and the reaction mixture was stirred at reflux for one-half hour, after which 99.2 parts of cyclohexylamine were added and the mixture was stirred at the boil for 19 hours. The nitrogen purge was discontinued and the charge was treated with 2.25 parts of sodium m-nitrobenzenesulfonate and stirred in air at the reflux temperature for 1 hour. After the charge had cooled to room temperature, the solids were isolated by filtration, washed successively with isopropanol, hot water, until the washings were neutral, and isopropanol, and dried. Yield of l,4-bis(cyclohexylamino)-5- aminoanthraquinone: 34.0 parts; m.p. 215-218C. Thin layer chromatography indicated small amounts of colored impurities in the blue product.

A solution of 4.46 parts of p-nitrobenzoyl chloride in 40 parts of nitrobenzene was added in portions to a mixture of 8 parts of the above 1,4- bis(cyclohexylamino)-5-aminoanthraquinone in 60 parts of nitrobenzene which was being stirred under ni- I trogen at 100C. After stirring for 1 hour, the reaction mixture was cooled to 80 C. and treated with 32 parts of ethanol. After the reaction mass had cooled to room temperature, the solids were isolated by filtration, washed with isopropanol and then with hot water, until the washings were neutral, and dried. Yield: 7.5 parts; m.p. 248-253C. After recrystallization from chloroform/isopropanol, the chromatographically pure, greenish blue dye had a m.p. of 260-262C. and exhibited absorptivities of 37.4 liters gm. cm? at 608 my, and 51.3 liters gm." cm." at 658 mu. Based on the above, the dye is l-(p-nitrobenzamido)-5,8-bis(cyclohexylamino)anthraquinone.

Dyes of similar dyeing and fastness properties can be prepared by the above procedures by replacing cyclohexylamine with molar equivalent quantities of dipropylamine or t-octylamine.

EXAMPLE 6 wherein R is mor p-nitrophenyl, and each X contains six to 18 carbon atoms and is NHalkyl, NHcyclohexyl, N(alkyl) or NHR wherein R is wherein a is H, alkyl or alkoxy, b is H, alkyl, alkoxy, F, Cl, Br, NHCOalkyl or NHCOR, and c is H, alkyl, alkoxy, F, Cl, Br, NHCOalkyl,

NHCOR, R, OR, NHR, CF CN, CONH CON- Halkyl, CON(alkyl) CONHR, CON(alkyl)R, SO NH SO NHalkyl, SO NHR, SO N(alkyl) SO N(alkyl)R, COalkyl, COR, CO alkyl, CO R, SO alkyl, R or N=NR, wherein R is phenyl or phenyl substituted with alkyl, alkoxy, halogen, CF or N0 provided that the 6- position of R is substituted with H, or if the 2- position is substituted with C alkyl, then H or (3 alkyl.

2. The dye of claim 1 wherein each X is p-toluidino and R is p-nitrophenyl.

3. The dye of claim 2 containing a minor amount of l-(p-nitrobenzamido)-4,5 ,8-tris(ptoluidino)anthraquinone.

4. The dye of claim 1 wherein each X is mchloroanilino and R is p-nitrophenyl, which dye contains up to 15 percent of l-(p-nitrobenzamido-4,5,8- tris(m-chloroanilino)anthraquinone.

5. The dye of claim 1 wherein each X is p-nbutylanilino and R is p-nitrophenyl.

6. The dye of claim 1 wherein each X is xylidino and R is p-nitrophenyl.

7. The dye of claim 1 wherein each X is cyclohexylamino and R is p-nitrophenyl. 

2. The dye of claim 1 wherein each X is p-toluidino and R1 is p-nitrophenyl.
 3. The dye of claim 2 containing a minor amount of 1-(p-nitrobenzamido)-4,5,8-tris(p-toluidino)anthraquinone.
 4. The dye of claim 1 wherein each X is m-chloroanilino and R1 is p-nitrophenyl, which dye contains up to 15 percent of 1-(p-nitrobenzamido-4,5,8-tris(m-chloroanilino)anthraquinone.
 5. The dye of claim 1 wherein each X is p-n-butylanilino and R1 is p-nitrophenyl.
 6. The dye of claim 1 wherein each X is xylidino and R1 is p-nitrophenyl.
 7. The dye of claim 1 wherein each X is cyclohexylamino and R1 iS p-nitrophenyl. 